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  • 1
    ISSN: 0935-6304
    Schlagwort(e): A,C- and A,D-bridged calix[6]arene ; stationary phase ; capillary gas chromatography ; geometric and positional isomer separation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---A,C-Bridged (ACCX) and A,D-bridged isopropyldimethylsilylcalix[6]arene (ADCX) dissolved in OV-1701 were used as stationary phases in isothermal capillary gas chromatographic separation of some positional isomers. Retention factors and separation factors for the isomers were measured. The isomers investigated are well resolved on the two phases. Retention of all the solutes investigated is longer on ACCX than on ADCX. The longer retention on A,C-bridged calix[6]arene is probably due to extra inductive interactions of the solute molecule with the carbonyl moieties in the phase. Separation factors for closely eluting isomer pairs are similar on the two phases. This seems to indicate that the carbonyl moieties do not play an appreciable role in discriminating the isomer molecules on entering the cavity of the calixarene if the solute is retained by the inclusion process.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 30 (1995), S. 969-976 
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Proton-transfer reactions that proceed within methanol cluster ions were studied using an electron impact time-of-flight mass spectrometer. When CH3OH seeded in helium is expanded and ionized by electron impact, the protonated species, (CH3OH)nH+, are the predominant cluster ions in the low-mass region. In CH3OD clusters, both (CH3OD)nH+ and (CH3OD)nD+ ions are observed. The ion abundance ratios, (CH3OD)nH+/(CH3OD)nD+, show a tendency to decrease as the methanol concentration increases, which is apparently related to the cluster structure and reaction energetics. The results suggest that the effective formation of (CH3OD)nH+ ions at low concentration of CH3OD in the expansion is the result of the relatively facile rotation of methanol molecules within the smaller clusters that tend to form at low CH3OD concentration. Ab initio molecular orbital calculations were carried out to investigate the rearrangement and dissociative pathways of ionized methanol dimer. Ion-neutral complexes, [CH3OH2+…O(H)CH2] and [CH3OH2+…OCH3], are found to play an important role in the low-energy pathways for production of CH3OH2+ + CH2OH (and OCH3) from ionized methanol dimer.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Reactions that proceed within mixed ethylene-methanol cluster ions were studied using an electron impact time-of-flight mass spectrometer. The ion abundance ratio, [(C2H4)n(CH3OH)mH+]/[(C2H4)n(CH3OH)m+], shows a propensity to increase as the ethylene/methanol mixing ratio increases, indicating that the proton is preferentially bound to a methanol molecule in the heterocluster ions. The results from isotope-labelling experiments indicate that the effective formation of a protonated heterocluster is responsible for ethylene molecules in the clusters. The observed (C2H4)n(CH3OH)m+ and (C2H4)n(CH3OH)m-1CH3O+ ions are interpreted as a consequence of the ion-neutral complex and intracluster ion-molecule reaction, respectively. Experimental evidence for the stable configurations of heterocluster species is found from the distinct abundance distributions of these ions and also from the observation of fragment peaks in the mass spectra. Investigations on the relative cluster ion distribution under various conditions suggest that (C2H4)n(CH3OH)mH+ ions with n + m ≤ 3 have particularly stable structures. The result is understood on the basis of ion-molecule condensation reactions, leading to the formation of fragment ions, \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm CH}_2=\!=\mathop {\rm O}\limits^ + {\rm CH}_3 $\end{document} and (CH3OH)H3O+, and the effective stabilization by a polar molecule. The reaction energies of proposed mechanisms are presented for (C2H4)n(CH3OH)mH+(n + m ≤ 3) using semi-empirical molecular orbital calculations.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 16 (1993), S. 289-298 
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective GC ; Polysiloxane-anchored cyclodextrin stationary phase ; Chirasil-Dex-TFA ; Immobilized 2,6-di-O-alkyl-3-O-acyl-cyclodextrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Heptakis(2,6-di-O-methyl-3-O-trifluoroacetyl)-†-cyclodextrin has been chemically bonded to a polydimethylsiloxane via an octamethylene spacer and subsequently immobilized on to the surface of fused silica capillaries, the first time a cyclodextrin derivative with mixed substituents has been immobilized in this way. The enantioselectivity of the new chiral stationary phase has been investigated as a function of the cyclodextrin content. It was found to be higher than that reported for heptakis (2,6-di-O-methyl-3-O-trifluoroacetyl)-†-cyclodextrin or hepta-kis(2,6-di-O-methyl-3-O-acetyl)-†-cyclodextrin dissolved in polysiloxane (e.g. OV-1701). The degree of immobilization was over 90 %. The temperature stability is, however, inferior to that of Chirasil-Dex (a permethylated cyclodextrin): the maximum operating temperature is approximately 200 °C.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 16 (1993), S. 215-223 
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective capillary (open-tubular) SFC ; Polysiloxane-anchored cyclodextrin stationary phase ; Immobilized Chirasil-Dex ; Separation of cyclodextrin derivatives by SFC ; Non-steroidal anti-inflammatory drugs (NSAIDs) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Immobilized polysiloxane-anchored permethyl-β-cyclodextrin (Chirasil-Dex) with a cyclodextrin content of approximately 30 % by weight, previously employed as a versatile chiral stationary phase for the separation of enantiomers by GC, has been used for the separation of enantiomers by capillary supercritical fluid chromatography (SFC). A considerable number of racemates could be resolved, e.g. aromatic alcohols, amino alcohols (TFA derivatives), and underivatized acids. Many pharmaceutical compounds were among those analyzed, including several NSAIDs (e.g. ibuprofen and ketoprofen), a steroidal drug (nor-gestrel), a barbiturate (hexobarbital), and others.Among the racemates resolved were many which cannot be analyzed by GC owing to low volatility or decomposition at elevated temperatures. For two racemates, analysis temperature and mobile phase density were systematically varied to give constant analysis times or capacity factors k. Low temperatures (ca 60 °C) yielded the best separation in term of separation factor, α, or resolution, Rs, even though higher densities had to be used. In comparison with GC, capillary SFC was able to furnish higher separation factors and similar resolution. The applicability of capillary SFC for the analysis of mixtures of cyclodextrin derivatives, e.g. those used in the synthesis of Chirasil-Dex, was, furthermore, demonstrated.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    ISSN: 0935-6304
    Schlagwort(e): Capillary GC ; Enantiomer resolution ; Chiral stationary phase ; Derivated cyclodextrins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Three new β-cyclodextrin derivatives, heptakis(6-O-isopropyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, heptakis(6-O-thexyldi-methylsilyl-2,3-di-O-ethyl)-β-cyclodextrin, and heptakis(6-O-cy-clohexyldimethyl-2,3-di-O-ethyl)-β-cyclodextrin (IPDE-β-CD, TXDE-β-CD, and CHDE-β-CD), were synthesized and the enan-tioselectivities of these three CD derivatives and heptakis(6-O-tert-butyldimethylsilyl-2,3-di-O-ethyl)-β-cyclodextrin (TBDE-β-CD) were compared for GC separation of a range of chiral test com-pounds. In particular TXDE-β-CD showed much higher enentio-selectivity than TBDE-β-CD. Enentioselectivities of IPDE-β-CD and CHDE-β-CD are somewhat lower than that of TXDE-β-CD and CHDE-β-Cd are somewhat lower than that of TXDE-β-CD. These observations are indicative of significant effects of subtle changes in the structure of the 6-O-substituent on the enantioselec-tivity of the β-CD derivatives. The difference in enantioselectivities of the 6-O-substituted CD derivatives were explained in terms of relative contributions of the effects of hydrophobicity and steric hindrance of the substituent to the inclusion process. CHDE-β-CD showed the lowest enantioselectivity among the threederivatives. It is likely that the unfavorable steric hindrance of the bulky cyclo-hexyl group plays a greater role than the favorable hydrophobicity effect of the cyclohexyl group in the inclusion process in CHDE-β-CD. IPDE-β-CD showed lower selectivity than TXDE-β-CD and TBDE-β-CD. In the case of these CD derivatives having acyclic substituents the relative hydrophobicity of the substituent seems to be a dominant factor affecting the inclusion process. Isopropyl groups factor affecting the inclusion process. Isopropyl groups are less hydrophobic than thexyl and tert-butyl groups.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 7
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective capillary gas chromatography ; Enantiomer separation of volatiles ; Cyclodextrin derivatives ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: High-resolution capillary gas chromatographic separation of enantiomers, belonging to different classes of compounds on cyclodextrin derivatives is described. The solutions of heptakis (2,3,6-O-trimethyl)-β-cyclodextrin (Phase I), heptakis (2,6-O-dimethyl-3-O-trifluoro-acetyl)-β-cyclodextrin (Phase II) and heptakis (2,6-O-dimethyl-3-O-heptafluorobutyryl)-β-cyclodextrin (Phase III) in the moderately polar polysiioxane OV-1701 were coated onto deactivated fused silica capillaries furnishing columns of high efficiency. The three phases show different enantioselectivities for various racemic mixtures.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 8
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective gas chromatography ; Polysiloxane-anchored cyclodextrin stationary phases ; Chirasil-Dex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 9
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 13 (1990), S. 748-753 
    ISSN: 0935-6304
    Schlagwort(e): LC-GC ; PAHs ; Glass, vial-shaped concentrator ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A new, versatile, and low cost on-line LC-GC interface has been devloped for the fast and reliable introduction of large volume samples into a cappillary GC column without using the conventional retention gap. PAHs in soot were analyzed by on-line normal phase HPLC-capillary GC. A glass, vial-shaped on-line concentrator provides a zone for solvent evaporation and sample concentration. Large volumes of HPLC eluate can be concentrated with the on-line concentrator and then transferred directly into the cappillary column. Trace levels (〈 10 ppb) of PAH compounds can be efficiently concentrated with the on-line concentrator and determined without loss or contamination.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 10
    ISSN: 0935-6304
    Schlagwort(e): Capillary gas chromatography ; Volatile halogenated hydrocarbons (VHH) ; Purge and trap technique ; Automated system ; Rainwater ; Ambient air ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: An automated system employing a purge and trap technique with capillary gas chromatography and electron-capture detection (ECD) has been developed for the analysis of trace levels of volatile halogenated hydrocarbons and applied to the determination of the compounds in environmental samples such as rainwater and ambient air. The operation of the method, its application to environmental samples, and the results obtained are described. Use of the system ensured good chromatographic resolution and high accuracy, even with trace levels of the compounds.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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